Method and apparatus of producing high-density polyidimide (HPI) film

ABSTRACT

The present invention relates to a method of producing high-density polyidimide (HPI) films and its production equipment. The production equipment comprises a raw material supplying means, a vacuum cavity, an energy supplier, a clad laminator, and a baked solidified polymer. The foregoing components constitutes the production equipment, using the monomer with the CONH bond or copolymer as raw materials to extract the unsaturated C═N bond by heat, electrons, light, radiation rays or ions as energy under low-pressure environment, so that the H in vacuum can extract the non-solidified HPI film from the electronic radical covalent polymers and via heat or light to rearrange the structure into a solidified HPI film. By means of the method according to the present invention, the original HPI that is not easily to produce as a film can be easily made in form of a film of HPI polymer on the clad laminator.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a method of producinghigh-density polyidimide (HPI) films and its production equipment. Theproduction equipment comprises a raw material supplying means, a vacuumcavity, an energy supplier, a clad laminator, and a baked solidifiedpolymer. The foregoing components constitute the production equipment,using the monomer with the CONH bond or copolymer as raw materials toextract the unsaturated C═N bond by heat, electrons, light, radiationrays or ions as energy under low-pressure environment, so that thehydrogen (H) in vacuum can extract the non-solidified HPI film from theelectronic radical covalent polymers and by using heat or light torearrange the structure into a solidified HPI film. By means of themethod according to the present invention, the original HPI that is noteasily to produce as a film can be easily made in form of a film of HPIpolymer on the clad laminator.

[0003] 2. Description of the Related Art

[0004] The present invention relates to a method of producing a polymerHPI film and its manufacturing equipment, more particularly to a methodand apparatus of producing a HPI polymer by plasma polymerization underlow-pressure environment.

[0005] Generally, a traditional film is coated by means of heating ormelting the solute and then coating it on a clad laminator surface.After it is cooled, and the solute is vaporized, it produces a film. Thetraditional HPI film is manufactured by chemical thermosetting process,unlike the traditional film coating method that simultaneously requiresthe processes of polymerization reaction and the coating for filmformation. Therefore, it needs higher technological capacity andstricter control on the parameters; furthermore, the equipment isexpensive. There are still some shortcomings such as a byproduct ofwater molecule (H₂O) is produced in the thermal imidization process, andthe HPI acid is converted into a HPI. Since the production of watermolecules affects the flatness of the film and causes pinholes anduneven thickness.

SUMMARY OF THE INVENTION

[0006] The primary objective of the present invention is to provide amethod of producing HPI polymer film compound.

[0007] The secondary objective of the present invention is to provide amethod of producing HPI polymer film.

[0008] Another objective of the present invention is to provide a methodof producing a HPI polymer with high-density and high-adhesivenesswithout any pinholes.

[0009] According to the above objectives, the method of the presentinvention comprises the steps of firstly providing a vacuum cavity asthe site for proceeding with the reaction; fixing a clad laminator inthe vacuum cavity; and activating, decomposing, and recombining thesubstance having a HPI bond such as the polymer or complex or covalentpolymer or monomers by controlling the parameters of the environmenttemperature, gas flow, voltage of the plasma, and current, etc. andusing an air extracting device to create a low-pressure environment toextract the hydrogen ion such that it produces a film having theactivated substance with unsaturated polymer HPI structure on thesurface of the clad laminator. Such activated substance could be an ionor a radical. The activated substance repeatedly proceeds with thecovalent polymerization in appropriate environment to produce a largerpolymer. In such a low-pressure environment, the gas remained after thereaction will be extracted quickly, thus facilitates the formation ofHPI. Therefore, the unsaturated HPI can be converted into HPIimmediately. The HPI film so produced will be subsided and accumulateddirectly on the surface of the solid clad laminator under thelow-pressure environment, and thus has a higher density, more even filmthickness with no pinholes, excellent adhesiveness on the cladlaminator, and better recurrence for the reaction. And then heat orlight incidence is added to produce the HPI film and rearrange thestructure into a high-density polymer and bake to solidify into a HPIfilm.

[0010] The device according to the present invention comprises a vacuumcavity for providing a low-pressure environment at least below 20 Torrsand preferably below 1 Torr; an energy supplier for supplying energy torepeatedly perform decomposition and recombination of the polymerizationto produce polymers. The form of supplied energy could be heat, light,electron collision, ion collision, and radiation ray, etc.; a rawmaterial supplying means for supplying raw materials of monomer,polymer, copolymer, or complex of polyidimide; a clad laminator tool forfixing the clad laminator in position, and the clad laminator could bemade of inorganic substance such as glass, ceramic, non-iron metal, ororganic polymer, etc. and could be designed as roll-to-roll tool orsheet-by-sheet tool.

[0011] Said device may further comprise an ultraviolet light incidentmeans or a heating means or both for providing the energy for promotingthe baking and a solidification of the polyidimide.

[0012] To make it easier for our examiner to understand the objective ofthe invention, its structure, innovative features, and its performance,we use a preferred embodiment together with the attached drawings forthe detailed description of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Other objects, features, and advantages of the invention willbecome apparent from the following detailed description of the preferredbut non-limiting embodiment. The description is made with reference tothe accompanying drawings, in which:

[0014]FIG. 1 shows the flowchart of the method of producing high-densitypolyidimide film according to the present invention.

[0015]FIG. 2 shows the cross-sectional diagram of the manufacturingequipment for producing high-density polyidimide film according to thepresent invention.

[0016]FIG. 3 shows the structure of an activated hollow ion gun.

[0017]FIG. 4A shows the flowchart of producing a high-densitypolyidimide film on a copper clad laminator according to the method andapparatus of the present invention.

[0018]FIG. 4B shows the cross-sectional diagram of the shapes of theproduct during different stages of producing a high-density polyidimidefilm on a copper clad laminator according to the method and apparatus ofthe present invention.

[0019]FIG. 5A shows the flowchart of producing a high-densitypolyidimide film on a glass clad laminator according to the method andapparatus of the present invention.

[0020]FIG. 5B shows the cross-sectional diagram of the shapes of theproduct during different stages of producing a high-density polyidimidefilm on a glass clad laminator according to the method and apparatus ofthe present invention.

NUMERAL DENOTATION FOR THE PARTS SHOWN IN THE FIGURES

[0021]201 Vacuum cavity

[0022]202 Extracting device

[0023]203 Energy supplier

[0024]204 Gas adjusting valve

[0025]205 Clad laminator

[0026]206 Tool

[0027]207 Heating device

[0028]208 Ultraviolet incident device

[0029]301 Copper cathode

[0030]302 Hollow pipe in the electrode

[0031]303 Target material

[0032]304 Magnetic terminal

[0033]305 Adjusting device

[0034]306 Electrode fixing block

[0035]307 Anode copper sing

[0036]308 Filament electrode

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0037] Please refer to FIG. 1 for the method of producing a polyidimidefilm according to a preferred embodiment of the present invention,comprising the steps of: firstly provide a clad laminator 101; puttingthe clad laminator into a vacuum cavity 102, and reducing, the pressureof the vacuum cavity and heat the vacuum cavity to a temperature of 103°C., wherein the so-called low temperature is about 2×10⁻⁵ torr, and thetemperature is about 160° C.; and then the substance with the structurecontaining the idimine is decomposed into smaller molecules by theenergy supplied by the energy supplier, and activated to produce theplasma 104, then the plasma is introduced into the hollow plasma coatinga film 105 on the clad laminator; finally restoring the pressure in thehollow cavity to normal pressure, and taking out the clad laminator forfurther heating procedure to bake and solidify the film 106.

[0038] An embodiment of the apparatus for producing a polyidimide filmaccording to the present invention having the elements as shown in FIG.2, comprising a hollow cavity 201 for providing a low-pressureenvironment and a site for the reaction; an air extracting means 202being coupled to the pipe leading to the hollow cavity 201 for providinga low pressure environment of less than 20 torr or even below 10⁻⁵ torr;an energy supplier 203, being coupled to the vacuum cavity 201 via thepipe for supplying the energy to repeatedly decompose and recombine thesubstance having the idimine structure for a chain reaction to form thepolymer; a gas adjusting valve 204 being connected to the energysupplier 203 to control the inflow gas such as the gas flow of thehydrogen, nitrogen, and oxygen gases; a clad laminator 205 beingdisposed inside the vacuum cavity 201 as a production site for the film,and its material could be inorganic matter such as glass, ceramic,non-iron metal, or organic polymer substance, etc, and also could be anintegrated circuit, or a printed circuit board; a tool 206 used to fixthe clad laminator 205 in position, and such tool can further comprisesa heating device 207 disposed inside the vacuum cavity 201, for heatingup the vacuum cavity 201 or providing energy to promote the formation ofpolyidimide and bake it for solidification, and said device furthercomprises an ultraviolet incident device 208 disposed in the hollowcavity to provide energy for promoting the formation of polyidimide andthe baking for solidification.

[0039] The foregoing energy supplier 203 could be an activated hollowion gun as shown in FIG. 3, comprising a copper cathode 301, having ahollow pipe 302 in the copper cathode 301 to facilitate the entrance ofthe gas, and the cathode 301 is embedded into the placing material tool,and this tool has a substance containing the idimine structure as atarget material 303, and the tool is controlled by the adjusting device305 to control the target material 303 in its rotation and feedingupward slowly; an anode copper ring 307 acts as the anode; a magneticelectrode disposed along the external rim of the anode copper ring 307forming a cavity; an electrode fixing block for fixing the electrode; amagnetic electrode disposed along the external rim of the copper anode307 for providing a magnetic field; a filament electrode 308 beingdisposed on the other end of the vacuum cavity, which could be anon-iron metal such as lead, palladium, nickel, and chromium, etc.

[0040] In FIG. 4A, it shows another embodiment of the method ofproducing the polyidimide film according to the present inventioncomprising the steps of: firstly providing a copper foil as the cladlaminator 205; preprocessing and rinsing; putting it on the tool 206 inthe vacuum cavity 201; then immediately heating the copper cladlaminator 205 to about 168° C.; extracting gas to reduce the pressure toabout 2×10⁻⁵ Torr; introducing hydrogen into the activated hollow iongun, and the pressure at the time is about 1 8×10⁻³ Torr, turning on theelectricity to start the ion collision on the polyidimide into smallmolecules to produce plasma; evaporating the polyidimide film attachedon the copper clad laminator and performing polymerization to producepolyidimine in gel form, and the parameters for the above environmentalconditions are as follows: the pressure from about 1 Torr to 4×10⁻³ Torrcan give the result of high-density polyidimide film, wherein the bestpressure is about from 5×10⁻² Torr to 2×10⁻³ Torr, and the second bestpressure is from about 1×10⁻¹ Torr to about 8×10⁻⁴ Torr. The bestpolymerization condition for the flow of the polyidimide molecules isabout 3×10⁻³ Torr, the second best is about 2×10⁻² Torr. The temperaturerange of the clad laminator under constant temperature is about 300° C.,wherein the best range is from about 150° C. to 180° C.; the second bestrange is from about 100° C. to 220° C., and then perform the manufactureprocess of pressing, baking, adding a protective coating, manufacturingin bars to produce the finished goods. The baking is done by theultraviolet lamp at about 300 nm to about 500 nm, and the diagram of itsstructure in different steps are shows in FIG. 4B

[0041] Another embodiment of the method of producing the polyidimidefilm according to the present invention as shown in FIG. 5A comprisesthe steps of: firstly providing an inorganic clad laminator such as apiece of glass; preprocessing and rinsing the glass putting the glass onthe tool and heating it to a temperature about 186° C. and reducing thepressure to about 2×10⁻⁵ Torr, and using the nitrogen or hydrogen toadjust the pressure to about 4.2×10⁻³ Torr; starting the power of theelectronic gun. By means of heating, it repeatedly decomposes andrecombines to form the polyidimide (PI) film by means of low-pressureand electron collision of hydrogen ion. The best conditions are asfollows: the temperature of the clad laminator is from about 150° C. toabout 180° C., and the second best is from about 120° C. to 200° C.Heating by resistors to provide the minimum energy sufficient fordecomposition of the molecules is the best. If the energy is too large,then it may decompose the produced polyidimide film back into H₂O andCO₂, and pulse discharge may be the best power used for the ion gun, andthe small molecule flow of the polyidimide is from 2×10⁻² Torr to 3×10⁻⁵Torr, the second best is from 1×10⁻¹ Torr to 1×10⁻³ Torr. Thepolyidimide so produced is in the form of transparent gel. After takingout from the nitrogen gas flow at 180° C., the baking for solidificationis performed to obtain the transparent polyidimide film, and finally ispackaged into finished goods. The structure at each stage is shown inFIG. 5B.

[0042] The method of the present invention can be used for the unevenaluminum clad laminator forming a polyidimide film with even thickness.In addition, it can also be used to produce the polyidimide film witheven thickness on the aluminum clad laminator of an IC required toshelter the α ray with a film of 50 μm thick.

[0043] The production of HPI in the form of non-solidified gel must bedone by the heat or violet ray to manufacture, rearrange, form a HPIwith high molecule weight and solidify around the rim, wherein theconditions of using heat or ultraviolet ray for baking to solidificationdepend on the selected type of PA raw materials. Frontier molecularorbital determines whether to use heat or ultraviolet, or both forbaking to solidification as an ideal mechanism in order to form asolidified HPI film of high molecular weight form the non-solidified HPIfilm. In general, the vacuum glow discharge under 1 Torr or below hassufficient distance for an acceleration such that the electron energycan easily reach the energy level of 2-5 eV, and the formation ofradical averages to about 3-4 eV, and the energy for forming ions isabout 9-12 eV, therefore under low-pressure vacuum, it easily torecombine into films of organic matters.

[0044] The following PA conversion or PI plasma polymerization isdescribed in the following PA that uses the follow as examples

NH(CH2)_(n−1)CO_(m)

[0045] where m is the number of polymers, n is the number of its acidicsalt such as PA-6, wherein n is equal to 6 then

[0046] When raw material PA is the generic name for chemical compoundhaving (—CONH—) bond. When the PA is decomposed under low-temperatureplasma, the tetrahedral PA compound normally select to keep the nitrogenradical and remove the hydrogen to form unsaturated C═N bond (the atomon the double-bonded molecules must be on the same plane), and theorganic matter generally does not have reduction, but is quite active inremoving the hydrogen, and the idimine products are not active becauseit has high production rate, and the C═O radical cannot be easilyradicalized because the conversion of C═O into C—O needs more energy(83.6 Kcal/mole). Therefore the polyidimide produces polymers with ionicbond, having the soluble property. Therefore, the mid-low temperatureplasma in the applied plasma chemistry can have good selectivity andhigh reaction rate, quick releasing speed, and the released film hasexcellent physical properties, and the chemical property of the cladlaminator has good adhesiveness and evenness. As to the generalpolymerization, the monomer should have special organic functionmechanism such as double bonds, etc., but as to the plasmapolymerization, it can have high molecular weight polymerization havingthe features as listed below: (1) it does not require catalyst, (2) highselectivity for material, (3) high density, (4) extremely thin with nodefective, (5) high heat-resistance temperature, and (6) even thickness,etc.

[0047] While the invention has been described by way of example and interms of a preferred embodiment, it is to be understood that theinvention is not limited thereto. To the contrary, it is intended tocover various modifications and similar arrangements and procedures, andthe scope of the appended claims therefore should be accorded thebroadest interpretation so as to encompass all such modifications andsimilar arrangements and procedures.

What is claimed is:
 1. A method of producing a high-density polyidimidefilm and its manufacturing equipment, said method comprising at least aclad laminator tool; a vacuum cavity; a raw material supplying means; anenergy supplier forming a manufacturing equipment, using a substancecontaining an idimine bond as initial material, applying a plasma toprovide an energy level under low-pressure vacuum for the decompositionof the substance into molecules; and then by means of the extraction ofhydrogen, it produces an activated species (ionic bond or radical); andthen performing polymerization again to form a non-solidifiedhigh-density polyidimide film on said clay laminator.
 2. A method ofproducing a high-density polyidimide film and its manufacturingequipment as claimed in claim 1, wherein said method further comprisinga baking to solidification device for performing a baking tosolidification step such that the non-solidified high-densitypolyidimide film is baked to solidify and to form the solidified HPIfilm.
 3. A method of producing a high-density polyidimide film and itsmanufacturing equipment as claimed in claim 1; wherein said initialmaterial is a polyidimide or its preliminary monomer or copolymer orcomplex compound having two or more polyidimides as the raw materialunder low-pressure vacuum environment, and by means of thelow-temperature plasma re-polymerization by heat, electron, light, andradiation ray ion to react and produce the high-density polyidimidecompound using

that contains other complex or copolymer of high-density polyidimidecompound.
 4. A method of producing a high-density polyidimide film andits manufacturing equipment as claimed in claim 1, wherein said cladlaminator is made of non-iron metal
 5. A method of producing ahigh-density polyidimide film and its manufacturing equipment as claimedin claim 1; wherein said clad laminator is made of glass.
 6. A method ofproducing a high-density polyidimide film and its manufacturingequipment as claimed in claim 1; wherein said clad laminator having asurface made of organic macromolecule.
 7. A method of producing ahigh-density polyidimide film and its manufacturing equipment as claimedin claim 1; wherein said clad laminator is made of inorganic material.8. A method of producing a high-density polyidimide film and itsmanufacturing equipment as claimed in claim 1; wherein said cladlaminator is an integrated circuit.
 9. A method of producing ahigh-density polyidimide film and its manufacturing equipment as claimedin claim 1; wherein said clad laminator is a printed circuit board. 10.A method of producing a high-density polyidimide film and itsmanufacturing equipment as claimed in claim 1; wherein said low-pressureenvironment having a pressure range from about 20 torrs to about 10⁻⁵torr.
 11. A method of producing a high-density polyidimide film and itsmanufacturing equipment as claimed in claim 1; wherein said step ofproviding an energy level is by heating, incidence of light, incidenceof radiation ray, collision of electrons, or collision of ions, or acombination of the foregoing forms.
 12. A method of producing ahigh-density polyidimide film and its manufacturing equipment as claimedin claim 2, wherein said solidification step is performed by heating.13. A method of producing a high-density polyidimide film and itsmanufacturing equipment as claimed in claim 2, wherein saidsolidification step is performed by the incidence of an ultravioletlighting device.
 14. A method of producing a high-density polyidimidefilm and its manufacturing equipment as claimed in claim 1; wherein saidsubstance having the idimide bond comprises the polyidimide, copolymerof polyidimide, complex compound of polyidimide, or monomer having theidimide bond.
 15. A manufacturing equipment for producing a high-densitypolyidimide film, comprising: a vacuum cavity for providing alow-pressure environment of 20 torrs or below as a container for thereaction; a raw material supplying means for supplying raw material thatcontains the substance with idimide bond; an energy supplier beingdisposed in the vacuum cavity to provide energy for the decomposition,repeated decomposition, and recombination of the raw material, a cladlaminator tool, being disposed in the vacuum cavity for fixing the cladlaminator in position.
 16. A manufacturing equipment for producing ahigh-density polyidimide film as claimed in claim 15, further comprisingan ultraviolet light incident device being disposed in the vacuum cavityor outside the vacuum cavity and providing the energy for thesolidification reaction.
 17. A manufacturing equipment for producing ahigh-density polyidimide film as claimed in claim 15, further comprisinga heating device being disposed in the vacuum cavity or outside thevacuum cavity and providing the energy for the solidification reaction.18. A manufacturing equipment for producing a high-density polyidimidefilm as claimed in claim 15, further comprising an ultraviolet lightincident device and a heating device being disposed in the vacuum cavityor outside the vacuum cavity and providing the energy for the reaction.